Networks containing perfluorocarbon organosilicon hyperbranched polymers

ABSTRACT

The present invention relates to hyperbranched copolymer networks containing hyperbranched copolymers that have perfluorocarbon and organosilicon entities that have high hydrophobicity, or high oleophobicity, or high thermal stability, or good adhesion to substrates, or any combinations thereof. This invention provides a further desirable combination of properties that include solubility before crosslinking, chemical resistance, and easy processibility. The copolymers may be crosslinked with a variety of crosslinking agents to give either rigid or elastomeric networks.

FEDERALLY SPONSORED RESEARCH STATEMENT

This invention was made with Government support under Award No.W31P4Q-05-C-R-114 from the Army, Department of Defense, to Oxazogen,Inc. as the award recipient and as its subcontractor to MichiganMolecular Institute. The Government has certain rights in thisinvention.

FIELD OF THE INVENTION

This invention concerns perfluorocarbon organosilicon polymer networkscontaining hyperbranched domains.

BACKGROUND OF THE INVENTION

The linear perfluorohydrocarbon polymer—polytetrafluoroethylene(PTFE)—is one of the most hydrophobic and oleophobic materials known andhas excellent thermal and chemical stability. [For example, see“Chemistry of Organic Fluorine Compounds II: A Critical Review” (ACSMonograph, ISSN 0065-7719; 187), edited by Milo{hacek over (s)}Hudlický/and Attlila E. Pavlath, 1995; and “Organofluorine Chemistry:Principle and Commercial Applications” edited by R. E. Banks, B. E.Smart, and J. C. Tatlow, 1994.] However, one disadvantage of PTFE isthat it cold flows under elevated pressure and/or temperature which haslimited its use in some applications, e.g., in the coating of bearings.[See U.S. Pat. Nos. 4,237,376 and 4,618,734.]

Additional disadvantages of PTFE are: a very high melting point of thecrystalline CF₂CF₂ chains that make it difficult to process; and itslack of solubility in commonly used solvents which limits itsapplication as a solution-born coating material. Also, PTFE cannot beused for liquid-based applications such as a lubricating fluid or as abase oil for greases.

These adverse effects which result from PTFE's crystalline nature havebeen alleviated by: a) reducing the crystallinity by copolymerizationwith other entities, or b) replacing some of the fluorine atoms in theC₂F₂ chain(s) with other groups. Examples of such copolymers arefluorinated ethylene propylene resins (FEP), perfluoroalkoxy resins(PFA), poly(chlorotrifluoroethylene)s (PCTFE), perfluorocarbon ethersand similar copolymers. However, incorporation of other entities to formcopolymers often adversely affects thermal properties, chemicalstability and the surface energy of the resulting materials to varying,and unpredictable degrees. For example, the incorporation of polargroups such as ethers, esters, amides or chlorine will reduce thehydrophobicity and oleophobicity of the copolymers. [For example, see“Chemistry of Organic Fluorine Compounds II: A Critical Review” (ACSMonograph, ISSN 0065-7719; 187), edited by Milo{hacek over (s)} Hudlickýand Attila E. Pavlath, 1995; and “Organofluorine Chemistry: Principleand Commercial Applications” edited by R. E. Banks, B. E. Smart, and J.C. Tatlow, 1994.] Copolymers that retain the CF₂ backbone can retainsome or most of the desirable properties of PTFE while improving otherproperties such as processibility, solubility, low T_(g) and the abilityto be crosslinked. Such a combination of properties makes thesematerials very interesting and provides many applications. Knowncopolymers that contain a CF₂ backbone have been limited to linearpolymers or to crosslined networks. [See U.S. Pat. Nos. 4,237,376 and4,618,734.]

Hydrophobic and oleophobic fluorocarbon networks made from smallmolecular fluorocarbons have been described, e.g., networks fromperfluoroalkylene acetylene compounds. [See U.S. Pat. Nos. 4,237,376 and4,618,734.] These compounds prior to curing are not polymers and arevolatile in high-temperature curing. Also, the viscosities of theirformulations are not readily adjustable.

Some curable linear fluorocarbon network-forming copolymers include theDuPont Fluoropolymer B (65% vinylidene fluoride, 25% tetrafluoroethyleneand 10% vinylbutyrate), the Abcite® and Lucite® fluoropolymers (based oncrosslinked mixtures of hydroxyl-fluoropolymers) and Lumiflon®fluoropolymer (a copolymer of tetrafluoroethlene with a monomer havinghydrophilic side groups). These fluorocarbon network-forming polymersgenerally contain polar groups.

Networks of hydrophobic hyperbranched polymers that contain siliconentities such as polycarbosiloxanes have been described [see U.S. Pat.Nos. 6,384,172 and 6,646,089], but networks of hyperbranchedperfluorocarbon polymers have not been reported.

BRIEF SUMMARY OF THE INVENTION

This invention relates to hyperbranched copolymer networks containingperfluorocarbon and organosilicon entities that have highhydrophobicity, or high oleophobicity, or high thermal stability or goodadhesion to substrates or any combinations of these properties. Thisinvention further provides a desirable combination of properties thatinclude solubility before crosslinking, chemical resistance, and easyprocessibility. Although such networks may contain polar groups (asdefined herein), preferably they are free of such polar groups.

These networks are prepared from hyperbranched polymers that containperfluorocarbon and organosilicon entities and a variety of crosslinkingagents and can be either rigid or elastomeric, with good adhesion tosubstrates. Furthermore, part of the hyperbranched polymer's multiplefunctionalities can be used for modifications that can provideadditional properties (such as crosslinkability without the need forcrosslinkers, or increased coating adhesion).

Such networks are expected to have applications in a variety ofdifferent fields including: high performance lithographic or printingcoatings, special adhesives, passivation layers for microprocesssors inelectronics, water-repellent and oil-resistant sealant gaskets,anti-icing coatings, finger-print free surfaces such as for cell-phonescreens, soil-resistant carpets, and high-performance elastomers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a comparison of water contact angles of the networks ofExample 15.

FIG. 2 shows TGA traces of coatings from a formulation of hyperbranchedpolycarbosiloxane that is designated as HBP—(SiOEt)-(SiMe₂H) and from aformulation of hyperbranched polyperfluorocarbon/siloxane that isdesignated as HBP-allyl[(CF₂)₆]—(SiMe₂H) in Example 15.

FIG. 3 shows methylene iodide contact angles of the coatings from aformulation of hyperbranched poly(perfluorocarbon/siloxane) that isdesignated as HBP-allyl[(CF₂)₆]—(SiMe₂H) and crosslinked with telechelicdiallyl polyfluorocarbon/siloxane (Example 16) and from a formulation ofhyperbranched polycarbosiloxane that is designated asHBP—(SiOEt)-(SiMe₂H) and crosslinked with telechelic divinylpolydimethylsiloxane (Example 15).

DETAILED DESCRIPTION OF THE INVENTION Glossary

The following terms as used in this application are to be defined asstated below and for these terms, the singular includes the plural.

-   -   “CA” means contact angle; desired is from about 95° to about        135° C.    -   “DSC” means Differential Scanning calorimetry    -   “FTIR” means Fourier Transform Infrared Spectroscopy    -   “GPC” means Gel Permeation Chromatography. Molecular weights        measured by GPC were calibrated with polystyrene standards using        PL gel 34-5/34-2 columns, toluene eluent and refractive index        detector    -   “HBP” means hyperbranched polymer; this is a specific class of        dendritic polymers and excludes dendrimers, dendrons, and        dendrigrafts    -   “hr” means hour(s)    -   “J” means coupling constant    -   “min” means minute(s)    -   “M_(n)” means number average molecular weight    -   “M_(w)” means weight average molecular weight    -   “PCTFE” means poly(chlorotrifluoroethylene)    -   “FEP” means fluorinated ethylene propylene resin    -   “PFA” means perfluoroalkoxy resin    -   “polar groups” means ether, ester, amine, urea, and hydroxyl        moieties    -   “PTFE” means polytetrafluoroethylene; a linear polymer    -   “RT” means ambient temperature or room temperature, from about        22 to about 25° C.    -   “sec” means second(s)    -   “solvents” means a liquid that can dissolve the HBP copolymer        having perfluorocarbon and organosilicon entities; examples are        organic solvents such as hexane, diethyl ether, acetone,        dichloromethane, tetrahydrofuran and chloroform. Depending on        the polar group content of and location on the HBP, other more        polar solvents, such as isopropanol, may be used    -   “T_(g)” means glass transition temperature that is defined in        ASTM D3417, D3418 and E1356; “low Tg” means in the range of        about −120° C. to about 25° C.    -   “TGA” means Thermal Gravimetric Analysis    -   “THF” means tetrahydrofuran    -   “T_(m)” means melting temperature

This invention relates to networks of hyperbranched copolymerscontaining perfluorocarbon and organosilicon entities that have highhydrophobicity, or high oleophobicity, or high thermal stability, orgood adhesion to substrates, or any combinations thereof.

The hyperbranched perfluorocarbon/silicone copolymers of the presentinvention have excellent processibility and solubility properties andhave the flexibility to be modified to convey other desired propertiesthat provide for many applications.

Additionally, soluble, hydrophobic and oleophobic multi-functionalizedhyperbranched copolymers containing fluorocarbon scaffold are ofinterest. They are readily crosslinked by known methods to formthermally-stable, hydrophobic and oleophobic network materials. Thisinvention utilizes such hyperbranched copolymers containingperfluorocarbon and organosilicon entities to form hydrophobic,oleophobic and/or thermally stable networks. The present networks highhydrophobicity is shown by the water contact angle of the networksurface in the range of about 95° to about 135°. The high oleophobicityof the present networks is shown by the CH₂I₂ contact angle of thenetwork surface of >90°. The present networks high thermal stability isshown by lack of degradation below 150° C. These hyperbranchedcopolymers have a glass transition temperature in the range from about−120° C. to about 25° C.

The crosslinking process can be solvent born or not; (e.g., where atleast one of the reactants are liquids). Additionally, the hyperbranchedcopolymer is soluble before crosslinking and is readily processed. Whenthe hyperbranched copolymers contain appropriate reactive functional endgroups, they can be crosslinkable by light, heat, moisture, radiation orcatalysis. The networks from hydrophobic hyperbranched polymerscontaining silicon entities such as polycarbosiloxanes have beendisclosed (U.S. Pat. Nos. 6,384,172 and 6,646,089), but networksprepared from hydrophobic and oleophobic hyperbranched polymerscontaining a perfluorocarbon scaffold have not been reported. Suchmaterials would have both hydrophobic and oleophobic properties and bemore thermal stability than the networks from hyperbranchedpolycarbosiloxane resins. Part of the functionalities on thehyperbranched polymer surface can also be available for surfaceadhesion. Good surface adhesion at room temperature will be manifestedby any of the following properties: not an easy release of the coatingfrom the surface of the substrate, not an easy scrape-off of the coatingfrom the surface of the substrate, difficult peel-off of the coatingfrom the surface of the substrate, and long-term retention of any of theformer properties.

The present invention uses hydrophobic and oleophobic,multi-functionalized hyperbranched perfluorocarbon/siloxane polymersincluding those that are free of polar groups. The polymers can readilybe cross-linked to form thermally stable, chemically-resistant,hydrophobic and oleophobic networks by hydrosilylation reactions wellknown in this art. Part of the functionalities on the hyperbranchedpolymer surface can also be available for surface adhesion. Thehyperbranched perfluorocarbon/siloxane polymers can be prepared as shownbelow in Scheme 1 for the synthesis of hyperbranchedperfluorocarbon/siloxane polymers from divinylperfluoroalkane and inScheme 2 for the synthesis of hyperbranched perfluorocarbon/siloxanepolymers from diallyl perfluoroalkanes. The reactions shown in bothschemes are carried to complete consumption of the minor components.

The hyperbranched polymers containing the —SiMe₂H chain ends in Schemes1 and 2 were prepared by a hydrosilylation reaction using a bimolecularpolymerization approach. By this approach [see U.S. Pat. No. 6,384,172]hyperbranched polymers are prepared by the reaction of multi-functionalA and B monomers, e.g., A₂+B₃, or generically A_(x)+B_(y), where x≧2 andy≧3. In order to avoid crosslinking to form gels, the polymerizationconditions must be controlled such that rp²≦1/[(x−1)(y−1)], where r isthe stoichiometric molar ratio of the reacting functionalities (i.e.,r=[A]/[B]) and p is the extent of the reaction determined with respectto the lesser component. Such polymerization conditions assume that allfunctional groups of the same type are equally reactive, and that nocyclization and no side reactions occur. In practice, there aredeviations from the theoretical r and p value for the critical gelpoint. Hyperbranched polymers can have A chain ends or B chain ends orboth depending on which component is in excess and the extent ofreaction p. Therefore, vinyl-ended hyperbranched(perfluorocarbon-siloxane) polymers can also be made from the samereactions as shown in Schemes 1 and 2 by using an excess of vinyl- orallyl-containing monomers.

In one aspect of Schemes 1 and 2, processes for preparing hyperbranchedcopolymers were done by reacting an organosilicon monomer containing—SiR₁R₂H groups, where R₁ and R₂ are independently alkyl, alkoxyl or H,and a perfluoroalkane containing allyl or vinyl functionalities, whereinthe number of SiH or allyl (vinyl) functionalities must be equal to orgreater than 2 and one must be equal to or greater than 3. In anotheraspect, reaction of organosilicon monomers containing vinyl or allylfunctionalities, and perfluoroalkane monomers containing —SiR₁R₂Hgroups, where R₁ and R₂ are alkyl, alkoxyl or H, wherein the number ofSiH or allyl (vinyl) functionalities must be equal to or greater than 2and one must be equal to or greater than 3. In a further aspect,hyperbranched copolymers were prepared from organosilicon monomerscontaining —SiR₁R₂H groups, where R₁ and R₂ are alkyl, alkoxyl or H, andperfluoroalkane monomers containing vinylether (CH₂═CHO—) or allylether(CH₂═CHCH₂O—) groups, wherein the number of SiH or allyl (vinyl)etherfunctionalities must be equal to or greater than 2 and one must be equalto or greater than 3.

According to a study by Guida-Pietasata (B. Ameduri, et al., J. Polym.Sci: Part A: Polym Chem, 1996, 34, 3077-3090), there can be a sidereaction of reverse hydrosilylation addition of the silyl group on thebeta position of the double bond and subsequent elimination of the silylgroup with a neighboring fluorine atom to generate small amounts of—CF═CH—CH₃. This was the case with hyperbranched(perfluorocarbon-siloxane) polymers made by hydrosilylation ofdivinylfluoroalkanes. The structures of the HBP—[(CF₂)_(n)]—(SiMe₂H)(n=4, 6, 8) polymers shown in Scheme 1 are ideal structures. The actualhyperbranched polymers will have small concentrations of defect brancheswith —CF═CH—CH₃ chain ends from these side reactions and segments fromsubsequent side reactions of the —CF═CH—CH₃.

In contrast to the hyperbranched polymers from divinylfluoroalkanes, thehyperbranched polymers HBP-allyl[(CF₂)_(n)]—(SiMe₂H) fromdiallylfluoroalkanes in Scheme 2 did not have the —CF═CH—CH₃ defectstructures because allyfluoroalkanes do not undergo such side reactions.

The functional end-groups of hyperbranched (perfluorocarbon-siloxane)polymers can be converted to other functionalities such asalkoxysilanes, silanol or acrylates that can self-crosslink to formnetworks. For example, the HBP-allyl[(CF₂)_(n)]—(SiMe₂H) has beenmodified with vinyltrimethoxysilane and vinyltriethoxysilane as shown inScheme 3 below (see Example 7 and 8 below) to give end-cappedhyperbranched (perfluorocarbon-siloxane) polymers that crosslink to formnetworks via the condensation reaction of silanols formed by thehydrolysis of alkoxysilanes (see Example 14 below and Scheme 3).

The hyperbranched (perfluorocarbon-siloxane) polymers can also becrosslinked with small molecular crosslinkers. For example,HBP—[(CF₂)_(n)]—(SiMe₂H) can be crosslinked withCH₂═CHCH₂(CF₂)_(n)CH₂CH═CH₂ (n=4-20) by a hydrosilylation reaction toform a network.

The hyperbranched (perfluorocarbon-siloxane) polymers can also becrosslinked with another hyperbranched (perfluorocarbon-siloxane)polymer. For example, HBP-[(CF₂)_(n)]—(SiMe₂H) can be crosslinked withHBP—[(CF₂)_(n)]-(Allyl)(n=4, 6, 8) by a hydrosilylation reaction.

The hyperbranched (perfluorocarbon-siloxane) polymers can be crosslinkedwith hydrophobic telechelic linear polymers. For example,HBP-allyl[(CF₂)_(n)]—(SiMe₂H)(n=6, 8) have been crosslinked withtelechelic divinyl polydimethylsiloxane to form hydrophobic networks.These are shown by Example 15 below.

HBP-allyl[(CF₂)_(n)]—(SiMe₂H)(n=6) was also crosslinked with linearpolymers containing fluorocarbon entities, such as the telechelicdiallyl poly(perfluoroalkane-siloxane). As shown by Example 16 below.

A series of such telechelic diallyl poly(perfluoroalkane-siloxane)s weresynthesized as shown in Scheme 4 below for crosslinking reactions withhyperbranched (perfluorocarbon-siloxane) polymers. These are shown byExamples 9, 10 and 11 below.

Hydrido-terminated (HMe₂Si) telechelic linearpoly(perfluoroalkane-siloxane)s can also be prepared by using excessdihydridosiloxane in the reaction shown in Scheme 4. Thehydrido-terminated linear polymer can be used to crosslink vinyl- and/orallyl-terminated hyperbranched (perfluorocarbon-siloxane) polymers toform networks.

The above-described networks can also be prepared using hyperbranchedpolymers such as hyperbranched (perfluoroether-siloxane) polymersprepared by the hydrosilylation reaction of perfluoro diallyl etherCH₂═CHCH₂O(CF₂)₂OCH₂CH═CH₂ with hydridosilane or hydridosiloxanecontaining 3 or more SiH groups. [See US Published Application2006/01474141 A 1 for the teaching of these hyperbranched polymers.]

EXAMPLES

The invention will be further clarified by a consideration of thefollowing examples, which are intended to be purely exemplary of thepresent invention.

Example 1 Synthesis of hyperbranched (perfluorocarbon/siloxane) polymersHBP-[(CF₂)_(n)]—(SiMe₂H)(n=4) using 1,4-divinyloctafluorobutane (A₂) andtetrakis(dimethylsiloxy)silane (B₄) with [B₄]/[A₂] ratio of 1.3

A 50 mL round-bottom flask equipped with a vertical cooling condenserwas charged with 1,4-divinyloctafluorobutane (2.52 g, 85.5%, 8.50 mmol),tetrakis (dimethylsiloxy)silane (3.77 g, 97%, 11.13 mmol) and 10 mL ofanhydrous THF. It was flushed and then stirred under N₂ for 5 min. Tothe reaction mixture was added 12.5 mg of the Karstedt's catalyst (˜2%platinum-divinyltetramethyldisiloxane complex in xylene) which was thenstirred at RT for 1 hr, followed by heating in an oil bath at 50° C. for2 days and to 65° C. for another 16 hrs. The volatiles were thenstripped off in a rotary evaporator. The product was washed withanhydrous acetonitrile (3×10 mL). Each time, the solution was pre-cooledwith a dry ice bath before the acetonitrile was decanted from theproduct phase. The volatiles were stripped off in a rotary evaporator atRT, and the resulting colorless viscous oil product was further dried ina vacuum overnight. A viscous colorless oil designated asHBP—[(CF₂)_(n)]—(SiMe₂H) (n=4) (1.3 g) was obtained. Its spectral andother data were as follows:

IR on KBr disc (selected peaks in cm⁻¹): 2963, 2902, 2867, 2134 (SiH),1712 (trace), 1311, 1259, 1204, 1158, 1075 (broad), 903, 840, 772, 719,625;

¹H NMR (CDCl₃, selected peaks in ppm): (1) Peaks assigned to the idealpolymer structure from hydrosilylation reaction: 0.16 (s, SiCH₃), 0.17(s, SiCH₃), 0.20 (s, SiCH₃), 0.25-0.26 (m, SiCH₃), 0.96 (t, ³J 7.3 Hz,CF₂CH₂CH₂Si), 1.66 (b, CF₂CH₂CH₂Si), 4.77 (septet, 4.77, ³J 2.6 Hz,SiMe₂H); (2) Unidentified peaks from the side reaction: 0.93-0.98 (m),1.60-1.25 (m), 3.4-3.8 (m), 3.73 (t, J: 0.022 Hz);

¹⁹F NMR (CDCl₃, selected peaks in ppm): −114.94 (s), −116.67 (s),−117.56 (s), −123.84 (s), −124.10 (s), −125.46 (s), −131.38 (s), −132.82(s), −143.95 (s), −144.93 (s);

¹³C NMR (CDCl₃, selected peaks in ppm): —1.23 (s), —0.52 (s), —0.07 (s),0.24 (s), 0.33 (s), 0.60 (s), 0.76 (s), 7.34 (s), 13.83 (s), 19.01 (s),19.42 (s), 26.62 (s), 34.75 (s), 62.10 (s), 70.66 (s), 109.44 (s) 118.89(m);

GPC: M_(n)=2900, M_(w)=4300;

Polydispersity=1.5;

TGA (10° C./min. in air): 160° C. (onset of mass loss), 514° C. (50%mass loss), residue 39% at 900° C.; and

DSC (10° C./min. in N₂): Tg −113° C.

Example 2 Synthesis of hyperbranched (perfluorocarbon/siloxane) polymersHBP-[(CF₂)_(n)]—(SiMe₂H) (n=6) using 1,6-divinylperfluorohexane (A₂) andtetrakis(dimethylsiloxy)silane (B₄) with [B₄]/[A₂] ratio of 1.3

A 25 mL round-bottom flask equipped with a vertical cooling condenserwas charged with 1,6-divinylperfluorohexane (0.594 g, 97%, 1.63 mmol),tetrakis (dimethylsiloxy)silane (0.730 g, 97.1%, 2.16 mmol) and 2 mL ofTHF. It was flushed and then stirred under N₂ for 5 min. To the reactionmixture was added 11.5 mg of the Karstedt's catalyst (˜2%platinum-divinyltetramethyl-disiloxane complex in xylene). It wasstirred at RT for 1 hr, and then at 65° C. for 2 days. The volatileswere stripped off in a rotary evaporator. The product was washed withanhydrous acetonitrile (3×5 mL). Each time the solution was pre-cooledwith a dry ice bath before the acetonitrile was decanted from theproduct phase. The volatiles were stripped off in a rotary evaporator atRT, and the resulting colorless viscous oil was further dried in avacuum overnight. A viscous colorless oil designated asHBP—[(CF₂)_(n)]—(SiMe₂H) (n=6) (0.85 g) was obtained. Its spectral andother data were as follows:

IR on KBr disc (selected peaks in cm⁻¹): 2962, 2935, 2908, 2870, 2134(Si—H), 1712 (weak), 1449, 1386, 1261, 1196, 1073, 986, 906, 844, 801,771, 720, 620;

¹H NMR (CDCl₃, selected peaks in ppm): (1) Peaks assigned to the idealpolymer structure from hydrosililation reaction: 0.12-0.23 (m, SiCH₃),0.91 (t, ³J 7.3 Hz, CF₂CH₂CH₂Si), 2.05 (b, CF₂CH₂CH₂Si), 4.72 (septet,³J 2.84 Hz, SiMe₂H), (2) Unidentified peaks from the side reaction:0.42-0.83 (m), 1.32-1.77 (m), 3.40 (s), 3.42 (s), 3.67 (t, J 6.84 Hz),3.70-3.90 (m), 4.60 (s), 5.56 (quartet J 7.32 Hz), 5.67 (quartet, J 7.08Hz);

¹⁹F NMR (CDCl₃, selected peaks in ppm): −114.93 (s), −116.68 (s), 117.97(s), −122.42 (s), 123.94 (s), −124.71 (s), −131.31 (s), −133.37 (s);

¹³C NMR (CDCl₃, selected peaks in ppm): −1.39 (s), −1.32 (s), 0.64-0.64(m), 7.26 (s), 8.67 (s), 13.83 (s), 18.98 (s), 19.38 (s), 24.92-26.25(m), 26.57 (s), 27.92-31.90 (m), 34.69 (s), 62.07 (s), 67.78 (s), 70.64(s), 107.71-121.88 (m);

GPC: M_(n)=4400, M_(w)=13,000;

Polydispersity=3.0;

TGA (10° C./min. in air): 218° C. (onset of mass loss), 467° C. (50%mass loss), residue 22% at 900° C.; and

DSC (10° C./min. in N₂): Tg −88.5° C.

Example 3 Synthesis of hyperbranched (perfluorocarbon/siloxane) polymersHBP-[(CF₂)_(n)]—(SiMe₂H) (n=8) using 1,8-divinylhexadecafluorooctane(A₂) and tetrakis(dimethylsiloxy)silane (B₄) with [B₄]/[A₂] ratio of 1.5

A 25 mL round-bottom flask equipped with a vertical cooling condenserwas charged with 1,8-divinylhexadecafluorooctane (1.0029 g, 98%, 2.17mmol), tetrakis (dimethylsiloxy)silane (1.1616 g, 97.1%, 3.43 mmol) and5 mL of THF. It was flushed and then stirred under N₂ for 5 min. To thereaction mixture was added 14 mg of the Karstedt's catalyst (˜2%platinum-divinyltetramethyl-disiloxane complex in xylene). It wasstirred at RT for 1 hr, and then at 80° C. for 2 days. The THF solventwas removed with a rotary evaporator at RT. The product was washed withanhydrous acetonitrile (3×5 mL). Each time, the solution was pre-cooledwith a dry ice bath before the acetonitrile was decanted from theproduct phase. The volatiles were stripped off in a rotary evaporator atRT, and the colorless viscous oil product designated asHBP—[(CF₂)_(n)]—(SiMe₂H) (n=8) was further dried in vacuum overnight. Aviscous colorless oil designated as HBP—[(CF₂)_(n)]—(SiMe₂H) (n=8) (0.85g) was obtained. Its spectral and other data were as follows:

IR on KBr disc (selected peaks in cm⁻¹): 2963, 2941 (shoulder), 2904,2872, 2134 (SiH), 1712 (weak), 1449, 1387, 1260, 1211, 1074, 904, 843,801, 772, 625;

¹H NMR (CDCl₃, selected peaks in ppm): (1) Peaks assigned to the idealpolymer structure from hydrosililation reaction: 0.14 (s, SiCH₃), 0.18(s, SiCH₃), 0.23 (SiCH₃), 0.93 (t, ³J 7.3 Hz, CF₂CH₂CH₂Si), 1.34-2.46(m, CF₂CH₂CH₂Si and entities from side reactions), 4.74 (septet, ³J, 2.6Hz, SiMe₂H), (2) Unidentified peaks from the side reaction: 0.76-0.86(m), 3.41-4.05 (m), 4.63 (s), 5.58-5.70 (m);

¹⁹F NMR (CDCl₃, selected peaks in ppm): −114.88 (s), −116.63 (s),−117.10 (s), −122.38 (s), −123.85 (s), −124.06 (s), −131.43 (s), −133.56(s);

¹³C NMR CDCl₃, selected peaks in ppm): −1.33, −0.779 (m), 7.25 (s), 8.67(s), 13.84 (s), 16.76 (s), 19.00 (s), 19.40 (s), 20.14 (s), 24.90 (s),25.21 (s), 25.52 (s), 25.66 (s), 25.93 (s), 26.26 (s), 26.58 (s), 27.87(s), 28.17 (s), 28.46 (s), 28.94 (s), 29.26 (s), 30.92 (s), 31.31 (s),31.82 (s), 32.26 (s), 34.71 (s), 62.11 (s), 67.81 (s), 70.66 (s), 77.85(s), 107.26 (s), 121.90 (m), 132.07 (s);

GPC M_(n)=3900, M_(w)=10100;

Polydispersity=2.6;

TGA (10° C./min. in air): 315° C. (onset of mass loss), 453° C. (50%mass loss), residue 15% at 900° C.; and

DSC (10° C./min. −175° C. to 200° C. in N₂): a Tg was not observed.

Example 4 Synthesis of hyperbranched (perfluorocarbon/siloxane) polymersHBP-allyl[(CF₂)_(n)]—(SiMe₂H) (n=4) using4,4,5,5,6,6,7,7-octafluorodeca-1,9-diene (A₂) andtetrakis(dimethylsiloxy)silane (B₄) with [B₄]/[A₂] 1.5

A 50 mL round-bottom flask equipped with a vertical cooling condenserwas charged with 4,4,5,5,6,6,7,7-octafluorodeca-1,9-diene (1.0 g, 3.12mmol) and tetrakis (dimethylsiloxy)silane (1.61 g, 4.75 mmol) and 2 mLof THF. The mixture was flushed and then stirred under N₂ for 5 mins. Tothe mixture was added 0.0101 g of the Karstedt's catalyst (˜2%platinum-divinyltetramethyl-disiloxane complex in xylene). It wasstirred at RT for 20 min., then heated in an oil bath at 50° C. for 16hrs. THF was stripped off and the product was washed with anhydrousacetonitrile (5×10 mL). Each time, the solution was pre-cooled with adry ice bath before the acetonitrile was decanted from the productphase. The remaining volatiles in the product were stripped off in arotary evaporator at RT, and the resulting viscous oil productdesignated as HBP-allyl[(CF₂)_(n)]—(SiMe₂H) (n=4) was further dried in avacuum oven overnight. The yield was 1.83 g. {The same product can alsobe prepared via bulk reactions using Rh catalyst[chlorotris(triphenylphosphine)-rhodium].} Its spectral and other datawere as follows:

IR on KBr disc (selected peaks in cm⁻¹): 2961, 2904, 2887, 2133 (SiH),1464, 1438, 1416, 1372, 1320, 1256, 1195, 1078, 905, 838, 799, 771, 628;

¹H NMR (CDCl₃, in ppm): 0.126 (s, SiCH₃), 0.132 (s, SiCH₃), 0.140 (s,SiCH₃), 0.206 (s, SiCH₃), 0.214 (s, SiCH₃), 0.223 (s, SiCH₃), 0.61-0.66(m, CF₂CH₂CH₂CH₂Si), 1.620-1.73 (m, CF₂CH₂CH₂CH₂Si), 2.02-2.31 (m,CF₂CH₂CH₂CH₂Si), 4.72 (m, SiMe₃H);

¹⁹F NMR (CDCl₃, in ppm): −115.00 (s, CF₂), −124.00 (s, CF₂);

¹³C NMR (CDCl₃, in ppm): −0.29 (s, SiCH₃), −0.27 (s, SiCH₃), −0.25 (s,SiCH₃), 0.31 (s, SiCH₃), 0.33 (s, SiCH₃), 14.46 (s, CF₂CH₂CH₂CH₂Si),17.86 (s, CF₂CH₂CH₂CH₂Si), 34.69 (t, ³J 22 Hz, CF₂CH₂CH₂CH₂Si), 109.14(t, J 33 Hz (CF₂)₄), 111.77 (t, J 33 Hz (CF₂)₄), 114.40 (t, J 33 Hz,(CF₂)₄), 115.86 (t, J 30 Hz), 118.39 (t, J 31 Hz, (CF₂)₄), (CF₂)₄),120.91 (t, J 31 Hz, (CF₂)₄);

²⁹Si NMR (CDCl₃, in ppm): −102.18 (s, Si(O—)₄), −102.57 (s Si(O—)₄),−102.86 (s, Si(O—)₄), −3.63 (s, OSiMe₂H), −3.51 (s, OSiMe₂H), −3.45 (s,OSiMe₂H), 10.24 (s, CH₂SiMe₂O), 10.37 (s, CH₂SiMe₂O), 10.51 (s,CH₂SiMe₂O);

GPC: M_(n)=3700, M_(w)=8300;

Polydispersity=2.3;

TGA (10° C./min. in air): 373° C. (onset of mass loss), 509° C. (50%mass loss), residue 40% at 900° C.;

DSC (10° C./min. in N₂): Tg −89° C.

Example 5 Synthesis of hyperbranched (perfluorocarbon/siloxane) polymersHBP-allyl[(CF₂)_(n)]—(SiMe₂H) (n=6) using4,4,5,5,6,6,7,7,8,8,9,9-Dodecafluoro-1,11-dodecadiene (A₂) andtetrakis(dimethylsiloxy)silane (B₄) with [B₄]/[A₂] 1.5

4,4,5,5,6,6,7,7,8,8,9,9-Dodecafluoro-1,11-dodecadiene (1.264 g)(prepared using a method adapted from the literature [A. Manseri, etal., J. Fluorine Chem. 73, 151-158 (1995)] was weighed into around-bottomed flask equipped with a cooling condenser.Tetrakis(dimethylsiloxy)silane (Gelest SIT7278.0, 1.7027 g) was added,followed by 1 mL of THF. The mixture was flushed and then stirred underN₂ for 5 mins. To the mixture was added 0.0107 g of the Karstedt'scatalyst (˜2% platinum-divinyltetramethyl-disiloxane complex in xylene).The mixture was stirred at RT for 20 min, then heated in an oil bath at50° C. for 16 hrs. The THF solvent was stripped off and the product waswashed with anhydrous acetonitrile (5×10 mL). Each time, the solutionwas pre-cooled with a dry ice bath before the acetonitrile was decantedfrom the product phase. The remaining volatiles in the product phasewere stripped off in a rotary evaporator at RT, and the resultingviscous oil product designated as HBP-allyl[(CF₂)_(n)]—(SiMe₂H)_(m′)(n=6) was further dried in a vacuum oven overnight. The yield was 1.7043g. {The same product can also be prepared via bulk reactions using Rhcatalyst [chlorotris (triphenylphosphine)-rhodium].} Its spectral andother data were as follows:

IR on KBr disc (selected peaks in cm⁻¹): 2961, 2904, 2891, 2134 (SiH),1464, 1416, 1377, 1321, 1256, 1203, 1075, 903, 799, 772, 630;

¹H NMR (CDCl₃, in ppm): 0.130 (s, SiCH₃), 0.136 (s, SiCH₃), 0.143 (s,SiCH₃), 0.208 (s, SiCH₃), 0.216 (s, SiCH₃), 0.224 (s, SiCH₃), 0.62-0.67(m, Si(CH₂CH₂CH₂CF₂)), 1.66-1.71 (m, Si(CH₂CH₂CH₂CF₂)), 2.07-2.11 (m,Si(CH₂CH₂CH₂CF₂)), 4.72-4.75 (m, SiMe₂H);

¹⁹F NMR (CDCl₃, in ppm): −124.24 (s, CF₂), −122.37 (s, CF₂), −114, 92(s, CF₂);

¹³C NMR (CDCl₃, in ppm): −0.30 (s, SiCH₃), −0.27 (s, SiCH₃), 14.41 (s,CF₂CH₂CH₂CH₂Si), 14.45 (s, CF₂CH₂CH₂CH₂Si), 17.84 (s, CF₂CH₂CH₂CH₂Si),34.59 (t, ³J 22.44 Hz, CF₂CH₂CH₂CH₂Si), 108.21-121.32 (m, (CF₂)₆);

²⁹Si NMR (CDCl₃, in ppm): −104.21 to −103.55 (m, Si(O—)₄), −4.91 to−4.68 (m, OSiMe₂H), 8.90 to 9.11 (m, CH₂SiMe₂O);

GPC: M_(n)=3800, M_(w=6400);

Polydispersity=1.7;

TGA (10° C./min. in air): 289° C. (onset of mass loss), 488° C. (50%mass loss), residue 36% at 900° C.; and

DSC (10° C./min. in N₂ from −90 to 259° C.): a Tg was not observed,T_(m) −62.5° C.

Example 6 Synthesis of hyperbranched (perfluorocarbon/siloxane) polymersHBP-allyl[(CF₂)_(n)]—(SiMe₂H) (n=8) using diallyl perfluorooctane (A₂)and tetrakis(dimethylsiloxy)silane (B₄) with [B₄]/[A₂] 1.5

Diallyl perfluorooctane CH₂═CHCH₂(CF₂)₈CH₂CH═CH₂ (0.5 g) (prepared usinga method adapted from the literature [A. Manseri, et al., J. of FluorineChem. 73, 151-158) (1995)] was weighed into a round-bottomed flaskequipped with a cooling condenser. Tetrakis(dimethylsiloxy)silane(Gelest SIT7278.0, 0.512 g) was added followed by 0.0074 g of Karstedt'scatalyst (˜2% platinum-divinyltetramethyl-disiloxane complex in xylene).The flask was flushed with nitrogen for 30 secs. The mixture was reactedat RT for 1 hr and then heated up in an oil bath at 50° C. overnight.The viscous oil was washed with anhydrous acetonitrile (5×5 mL) toremove unreacted reagents and low molecular weight entities and thendried using a rotary evaporator. The viscous oil product designated asHBP-allyl[(CF₂)_(n)]—(SiMe₂H) (n=8) was further dried under vacuum for 5hrs. The yield was 0.9 g. Its spectral and other data were as follows:

IR on KBr disc (selected peaks in cm⁻¹): 2962, 2903, 2887, 2805, 2134(SiH), 1464, 1438, 1418, 1377, 1323, 1256, 1213, 1163, 1150, 1076, 967,904, 839, 800, 772, 722, 700, 651, 628, 568, 556, 535;

¹H NMR (CDCl₃, in ppm): 0.144 (s, SiCH₃), 0.151 (s, SiCH₃), 0.215 (s,SiCH₃), 0.223 (s, SiCH₃), 0.229 (s, SiCH₃), 0.63-0.67 (m,Si(CH₂CH₂CH₂CF₂)), 1.69-1.72 (m, Si(CH₂CH₂CH₂CF₂)), 2.06-2.14 (m,Si(CH₂CH₂CH₂CF₂)), 4.73-4.75 (m, Me₂SiH);

¹⁹F NMR (CDCl₃, in ppm): −137.71 (s, CF₂), −137.57 (s, CF₂), −130.07 (s,CF₂ at chain end), −124.18 (s, CF₂), −123.96 (s, CF₂), −122.46 (s, CF₂),−122.29 (s, CF₂), −114.96 (s, CF₂);

¹³C NMR (CDCl₃, in ppm): −0.305 (s, SiCH₃), −0.30 (s, SiCH₃), 0.24 (s,SiCH₃), 0.28 (s, SiCH₃), 14.31 (s, CF₂CH₂CH₂CH₂Si), 14.35 (s,CF₂CH₂CH₂CH₂Si), 17.76 (s, CF₂CH₂CH₂CH₂Si), 34.44 (t, ³J 22.07 Hz,CF₂CH₂CH₂CH₂Si), 108.20-121.23 (m, (CF₂)₈);

²⁹Si NMR (CDCl₃, in ppm): −105.09 (s, Si(O—)₄), −6.03 to −5.9 (m,OSiMe₂H), 7.73 to 7.95 (m, CH₂SiMe₂O);

GPC: M_(n)=4400, M_(w)=15100;

Polydispersity=3.5;

TGA (10° C./min. in air): 302° C. (onset of mass loss), 468° C. (50%mass loss), residue 31% at 900° C.; and

DSC (10° C./min. in N₂ from −90 to 200° C.): a Tg was not observed,T_(m) 23° C.

Example 7 Modification of HBP-allyl[(CF₂)_(n)]—(SiMe₂H) (n=6) withvinyltrimethoxysilane

A 25 mL round-bottomed flask equipped with a vertical cooling condenserwas charged with 1.6448 g of HBP-(Allyl)[(CF₂)₆]—(SiMe₂H) and 1.707 gvinyl-trimethoxylsilane. It was flushed with N₂ and stirred for 5 mins.To the reaction mixture was added 0.0115 g of Karstedt's catalyst (˜2%platinum-divinyltetramethyl-disiloxane complex in xylene). It wasstirred at RT for 1 hr and then heated in an oil bath at 50° C. for 16hrs. IR of the crude product showed the SiH peak disappeared. Theviscous oil was washed with anhydrous acetonitrile (5×10 mL) and driedin a rotary evaporator. The viscous oil product designated asHBP-(Allyl)[(CF₂)₆]—[SiMe₂HCH₂CH₂Si(OMe)₃] was further dried undervacuum for 5 hrs. The yield was 1.20 g. Its spectral and other data wereas follows:

IR on KBr disc (selected peaks in cm⁻¹): 2918, 2957, 2841 (SiOCH₃),1463, 1439, 1410, 1377, 1324, 1256, 1195, 1141, 1088, 1003, 836, 798,735, 718, 692, 624, 604, 564, 535;

¹H NMR (CDCl₃, in ppm): 0.071 (s, SiCH₃), 0.074 (s, SiCH₃), 0.11 (s,SiCH₃), 0.12 (s, SiCH₃), 0.15 (s, SiCH₃), 0.56 (s, Si(C₂H₄)Si, 0.58-0.62(m, CF₂CH₂CH₂CH₂Si), 1.62-1.66 (m, CF₂CH₂CH₂CH₂Si), 2.1 (b,CF₂CH₂CH₂CH₂Si), 1.62-1.66 (m, CH₂SiCH—CH₃ from side reaction of reverseaddition); 3.55 (s, SiOCH₃);

¹⁹F NMR (CDCl₃, in ppm): −124.28 (s, CF₂), −122.42 (s, CF₂), −115.00 (s,CF₂);

¹³C NMR (CDCl₃, selected peaks in ppm): −1.096 (s, SiCH₃), −1.059 (s,SiCH₃), −1.044 (s, SiCH₃), −0.427 (s, SiCH₃), −0.412 (s, SiCH₃),0.54-0.79 (s, SiCH₃); 5.23 (s), 5.25 (s), 7.24 (s), 7.28 (s), 7.30 (s),8.76 (s, Si(C₂H₄)Si), 8.79 (s, Si(C₂H₄)Si), 14.25 (s, CF₂CH₂CH₂CH₂Si),17.75 (s, CF₂CH₂CH₂CH₂Si), 17.76 (a, CF₂CH₂CH₂CH₂Si), 34.35 (t, 22.07Hz, CF₂CH₂CH₂CH₂Si), 50.36 (s, SiOCH₃), 50.37 (s, SiOCH₃), 50.43 (s,SiOCH₃), 108.22-120.77 (m, (CF₂)₆);

²⁹Si NMR (CDCl₃, in ppm): −104.62 (m, Si(O—)₄), −41.57 (m, CH₂Si(OMe)₃),8.23-8.70 (m, CH₂SiMe₂O), 9.65-10.10 (m, CH₂SiMe₂O);

GPC: M_(n)=7600, M_(w)=13200;

Polydispersity=1.7;

TGA (10° C./min. in air): Initial mass loss at 7.7% before 200° C. dueto the unstable chain ends Si(OMe)₃, 228° C. (onset of decomposition),480° C. (50% mass loss), residue 34% at 900° C.; and

DSC (10° C./min. in N₂ from −90 to 200° C.): a Tg was not observed.

Example 8 Modification of HBP-allyl[(CF₂)_(n)]—(SiMe₂H) (n=6) withvinyltriethoxysilane

A 50 mL round-bottomed flask equipped with a vertical cooling condenserwas charged with 3.8 g HBP-(Allyl)[(CF₂)₆]—(SiMe₂H) and 5.2 g ofvinyltriethoxysilane. It was flushed with N₂ and stirred for 5 mins. Tothe reaction mixture was added 0.0245 g of Karstedt's catalyst (˜2%platinum-divinyltetramethyldisiloxane complex in xylene). It was stirredat RT for 1 hr and then heated in an oil bath at 50° C. for 16 hrs. IRof the crude product showed that the SiH peak had disappeared. Theviscous oil was washed with anhydrous acetonitrile (5×15 mL) and driedin a rotary evaporator. The viscous oil product designated asHBP-(Allyl)[(CF₂)₆]—[SiMe₂HCH₂CH₂Si(OEt)₃] was further dried undervacuum for 5 hrs. The yield was 3.8 g. Its spectral and other data wereas follows:

IR on KBr disc (selected peaks in cm⁻¹): 2974, 2927, 2886, 2735, 1483,1462, 1442, 1408, 1390, 1256, 1203, 1167, 1140, 1104, 1079, 996, 957,840, 788, 719, 692, 649, 625, 604, 585, 535;

¹H NMR (CDCl₃, in ppm): 0.047 (s, SiCH₃), 0.055 (s, SiCH₃), 0.77 (s,SiCH₃), 0.86 (s, SiCH₃), 0.094 (s, SiCH₃), 0.13 (s, SiCH₃), 0.14 (s,SiCH₃), 0.53 (s, Si(C₂H₄)Si), 0.56-0.60 (m, CF₂CH₂CH₂CH₂Si), 1.08 (d, ²J7.63 Hz, CH₂SiCH—CH₃ from side reaction of reverse addition); 1.15-1.20(m, OCH₂CH₃), 1.62-1.63 (b, CF₂CH₂CH₂CH₂Si), 2.01-2.05 (b,CF₂CH₂CH₂CH₂Si), 3.78 (quartet, ³J 7.00 Hz, SiOCH₂CH₃);

¹⁹F NMR (CDCl₃, in ppm): −124.31 (s, CF₂), −123.83 (s, CF₂), −122.45 (s,CF₂), −115.05 (s, CF₂), −113.81 (s, CF₂);

¹³C NMR (CDCl₃, selected peaks in ppm): −1.171 (s, SiCH₃), −1.096 (s,SiCH₃), −1.037 (s, SiCH₃), −0.494 to −0.367 (s, SiCH₃), 0.54 to 0.79 (s,SiCH₃); 1.78 (s, Si(C₂H₄)Si), 8.90 (s, Si(C₂H₄)Si), 8.93 (s,Si(C₂H₄)Si), 14.25 (s, CF₂CH₂CH₂CH₂Si), 17.71 to 17.87 (m,CF₂CH₂CH₂CH₂Si), 18.07 to 18.15 (m, OCH₂CH₃), 34.37 (t, ³J 22.67 Hz,CF₂CH₂CH₂CH₂Si), 58.21 (s with satellite peaks, OCH₂CH₃), 108.23-125.22(m, (CF₂)₆);

²⁹Si NMR (CDCl₃, in ppm): −115.55 to −102.48 (m, Si(O—)₄), −47.17 to−45.86 (m, CH₂Si(OEt)₃), 6.34 to 7.52 (m, CH₂SiMe₂O), 8.21 to 9.23 (m,CH₂SiMe₂O);

GPC: M_(n)=4400, M_(w)=5700;

Polydispersity=1.3;

TGA (10° C./min. in air): 209° C. (onset of mass loss), 440° C. (50%mass loss), residue 39% at 900° C. (10° C./min. in N₂ from −90 to 200°C.): a Tg was not observed.

Example 9 Attempted synthesis of linear poly(perfluorinatedalkane-dimethylsiloxane) —[C₄F₈C₃H₆(SiMe₂O)SiMe₂C₃H₆]_(n)— from4,4,5,5,6,6,7,7-octafluorodeca-1,9-diene and1,1,3,3-tetramethyldisiloxane

4,4,5,5,6,6,7,7-Octafluorodeca-1,9-diene (1.5 g, 4.67 mmol, 87.8%purity) was weighed into a round-bottomed flask equipped with a coolingcondenser. 1,1,3,3-tetramethyldisiloxane (0.68 g, 4.91 mmol, 97% purity)was added followed by 0.0104 g of Karstedt's catalyst (˜2%platinum-divinyltetramethyl-disiloxane complex in xylene). The flask wasflushed with nitrogen for several sec. The mixture was reacted at RT for1 hr and then heated in an oil bath at 50° C. for 3 days. The reactionwas allowed to cool to RT and the resulting mixture was examined by FTIRspectroscopy, which showed that the reaction did not go to completion asboth a vinyl and a SiH band remained although excess oftetramethyldisiloxane was used. The product appeared to be of very lowviscosity. GPC confirmed the molecular weight of the product was verylow, with M_(n)=1500 and M_(w)=1700, and a polydispersity=1.2. Thereaction when conducted in anhydrous THF gave a similar product.

Example 10 Synthesis of telechelic diallyl poly(perfluorinatedalkane-dimethylsiloxane)CH₂═CHCH₂[C₄F₈C₃H₆(SiMe₂O)₂SiMe₂C₃H₆]_(n)C₄F₈CH₂CH═CH₂ from4,4,5,5,6,6,7,7-octafluorodeca-1,9-diene and1,1,3,3,5,5-hexamethyltrisiloxane

It was found that the reactant 1,1,3,3-tetramethyldisiloxane was veryvolatile. This may have been the reason why the linear polymerization inExample 9 did not go to completion as the real reactant ratio may havedeviated from the mixing ratio. A modified polymerization usingnon-volatile 1,1,3,3,5,5-hexamethyltrisiloxane was then conducted.4,4,5,5,6,6,7,7-Octafluorodeca-1,9-diene (0.5 g, 1.755 mmol, 99% purity)was weighed into a round-bottomed flask equipped with a coolingcondenser. 1,1,3,3,5,5-Hexamethyltrisiloxane (0.38 g, 1.79 mmol, 98.4%purity) was added, followed by 1 mL of anhydrous THF and 0.0066 g ofKarstedt's catalyst (˜2% platinum-divinyltetramethyl-disiloxane complexin xylene). The flask was flushed with nitrogen for several sec. Themixture reacted at RT for 1 hr and then was heated in an oil bath at 50°C. overnight. The reaction was allowed to cool to RT and the resultingmixture was examined by FTTR spectroscopy, which was showed by theabsence of a Si—H band indicating that the reaction was complete. Theobtained reaction mixture was very viscous. All the volatiles wereremoved using a rotary evaporator. The viscous oil was washed withanhydrous acetonitrile (5×5 mL) and dried in the rotary evaporator. Theviscous oil product designated asCH₂═CHCH₂[C₄F₈C₃H₆(SiMe₂O)₂SiMe₂C₃H₆]_(n)C₄F₈CH₂CH═CH₂ was further driedunder vacuum for 24 hrs. The yield was 0.6872 g. Its spectral and otherdata were as follows:

IR on KBr disc (selected peaks in cm⁻¹): 2901, 2959, 2885, 2804, 1942(CH═CH₂), 1463, 1438, 1413, 1377, 1323, 1259, 1194, 1164, 1079, 1052,966, 910, 838, 799, 767, 710, 570, 533;

¹H NMR (CDCl₃, in ppm): 0.013 (s, SiCH₃), 0.076 (s, SiCH₃), 0.583 (t, J8.41 Hz, CF₂CH₂CH₂CH₂Si), 1.61-1.65 (m, CF₂CH₂CH₂CH₂Si), 1.96-2.14 (m,CF₂CH₂CH₂CH₂Si); 2.815 (doublet of triplet, ³J_(F,H) 18.39 Hz, ³H_(H,H)6.94 Hz, CH₂═CHCH₂CF₂); 5.27-5.32 (m, CH₂═CHCH₂CF₂), 5.63-5.85 (m,CH₂═CHCH₂CF₂),

¹⁹F NMR (CDCl₃, in ppm): −124.301 (s, CF₂), −124.271 (s, CF₂), −115.176(s, CF₂), −113.926 (s, CF₂);

¹³C NMR (CDCl₃, in ppm): 0.05 (s, SCH₃), 1.12 (s, SiCH₃), 14.44 (s,CF₂CH₂CH₂CH₂Si), 17.93 (s, CF₂CH₂CH₂CH₂Si), 34.46 (t, J 22.93 Hz,CF₂CH₂CH₂CH₂Si), 108.34-121.13 (m, (CF₂)₄);

²⁹51 NMR (CDCl₃, in ppm): −21.40 (s, Me₂Si(O—)₂), 5.86 (s, CH₂SiMe₂O—);

GPC: M_(n)=5700, M_(W)=9700;

Polydispersity=1.7;

TGA (10° C./min. in air): 283° C. (onset of mass loss), 350° C. (50%mass loss);

DSC (10° C./min. in N₂): Tg −77° C.

Example 11 Synthesis of telechelic diallyl poly(perfluorinatedalkane-dimethylsiloxane)CH₂═CHCH₂[C₆F₁₂C₃H₆(SiMe₂O)₂SiMe₂C₃H₆]_(n)C₆F₁₂CH₂CH═CH₂ from4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorododeca-1,11-diene and1,1,3,3,5,5-hexamethyltrisiloxane

4,4,5,5,6,6,7,7,8,8,9,9-Dodecafluorododeca-1,11-diene (0.5 g, 1.31 mmol)was weighed into a round-bottomed flask equipped with a coolingcondenser. 1,1,3,3,5,5-Hexamethyltrisiloxane (0.273 g, 1.29 mmol, 98.4%purity) was added, followed by 1 mL of anhydrous THF and 0.0060 g ofKarstedt's catalyst (˜2% platinum-divinyltetramethyldisiloxane complexin xylene). The flask was flushed with nitrogen. The mixture was reactedat RT for 1 hr, and then was heated in an oil bath at 50° C. overnight.The product was allowed to cool to RT and its FTIR spectrum wasobtained. The absence of a Si—H band indicated that the reaction wascomplete. The volatiles were removed using a rotary evaporator. Theresulting viscous oil, designated asCH₂═CHCH₂[C₆F₁₂C₃H₆(SiMe₂O)₂SiMe₂C₃H₆]_(n)C₆F₁₂CH₂CH═CH₂, was washedwith anhydrous acetonitrile (5×5 mL) and dried in a rotary evaporatorand then dried under vacuum for 24 hrs. The yield was 0.67 g. Itsspectral and other data were as follows:

IR on KBr disc (selected peaks in cm⁻¹): 2902, 2959, 2886, 2805, 1943,1648 (CH₂═CH), 1463, 1438, 1413, 1376, 1324, 1260, 1200, 1140, 1080,1052, 930, 841, 799, 768, 712, 692, 650, 561, 535;

¹H NMR (CDCl₃, in ppm): 0.019 (s, SiCH₃), 0.083 (s, SiCH₃), 0.592 (t, J8.51 Hz, CF₂CH₂CH₂CH₂Si), 1.60-1.68 (m, CF₂CH₂CH₂CH₂Si), 2.00-2.13 (m,CF₂CH₂CH₂CH₂Si); 2.827 (doublet of triplet, ³J_(F,H)) 18.29 (Hz,³J_(H,H) 7.04 Hz, CH₂HCH₂CF₂); 5.278-5.333 (m, CH₂═CHCH₂CF₂), 5.74-5.83(m, CH₂═CHCH₂CF₂);

¹⁹F NMR (CDCl₃, in ppm): −137.73 (s, CF₂), −137.59 (s, CF₂), −130.26 (s,CF₂), −124.32 (s, CF₂), −123.80 (s, CF₂), 122.41 (s, CF₂), −115.04 (s,CF₂), −113.78 (s, CF₂);

¹³C NMR (CDCl₃, in ppm): 0.05 (s, SCH₃), 1.07 (s, SiCH₃), 14.40-14.47(m, CF₂CH₂CH₂CH₂Si), 17.91 (s, CF₂CH₂CH₂CH₂Si), 34.38 (t, J 22.06 Hz,CF₂CH₂CH₂CH₂Si), 108.06-122.34 (m, (CF₂)₆);

²⁹Si NMR (CDCl₃, in ppm): −19.78 (s, Me₂Si(O—)₂, 7.40 (s, CH₂SiMe₂O—);

GPC: M_(n)=8200, M_(W)=13800;

Polydispersity=1.7;

TGA (10° C./min. in air): 296° C. (onset of mass loss), 377° C. (50%mass loss), residue 0.7% at 900° C.; and

DSC (10° C./min. in N₂): two melting peaks were observed at −28° C. andat 5.8° C.

Example 12 Synthesis of telechelic diallyl poly(perfluorinatedalkane-dimethylsiloxane)CH₂═CHCH₂[C₈F₁₆C₃H₆(SiMe₂O)₂SiMe₂C₃H₆]_(n)C₈F₁₆CH₂CH═CH₂ fromCH₂═CHCH₂(CF₂)₈CH₂CH═CH₂ and 1,1,3,3,5,5-hexamethyltrisiloxane

CH₂═CHCH₂(CF₂)₈CH₂CH═CH₂ (0.50 g, 1.04 mmol) was weighed into around-bottomed flask equipped with a cooling condenser.1,1,3,3,5,5-Hexamethyltrisiloxane (0.22 g, 1.04 mmol by 98.4% purity)was added followed by 1 mL of anhydrous THF and 0.0040 g of Karstedt'scatalyst (˜2% platinum-divinyltetramethyl-disiloxane complex in xylene).The flask was flushed with nitrogen for several secs. The mixture wasreacted at RT for 1 hr, and then in an oil bath at 50° C. overnight. Thereaction was allowed to cool to RT and a FTIR spectrum of the resultingmixture was obtained. It showed the reaction was complete based on theabsence of a Si—H band. All volatiles were removed using a rotaryevaporator. The resulting viscous oil designated asCH₂═CHCH₂[C₈F₁₆C₃H₆(SiMe₂O)₂SiMe₂C₃H₆]_(n)C₈F₁₆CH₂CH═CH₂ was washed withanhydrous acetonitrile (5×5 mL) and dried in a rotary evaporator andthen further dried under vacuum for 24 hrs. The yield was 0.65 g. Itsspectral and other data were as follows:

IR on KBr disc (selected peaks in cm⁻¹): 2960, 2886, 2805, 1943(CH₂═CHSi), 1463, 1438, 1414, 1375, 1323, 1276, 1260, 1213 (broad),1150, 1126, 1056 (broad), 914, 842, 801, 768, 701, 647, 619, 559, 533;

¹H NMR (CDCl₃, in ppm): 0.015 (s, SiCH₃), 0.073 (s, SiCH₃), 0.588 (t, J8.29 Hz, CF₂CH₂CH₂CH₂Si), 1.60-1.68 (m, CF₂CH₂CH₂CH₂Si), 2.01-2.11 (m,CF₂CH₂CH₂CH₂Si); 3.62-3.75 (m, CH₂═CHCH₂CF₂); 5.877 (t, J 5.23 Hz,C₂H₃CH₂CF₂), 6.006 (t, J 5.09 Hz, C₂H₃CH₂CF₂), 6.137 (t, J 5.18 Hz,C₂H₃CH₂CF₂);

¹⁹F NMR (CDCl₃, in ppm): −137.72 (weak, s, CF₂), −137.58 (weak, s, CF₂)−130.06 (weak, s, CF₂), −124.25, (s, CF₂), −123.95 (s, CF₂), −122.51(weak, s, CF₂) −122.32 (s, CF₂), −115.08 (s, CF₂);

¹³C NMR (CDCl₃, in ppm): −0.062 (s, SCH₃), 1.054 (s, SiCH₃), 14.40 and14.37 (s, CF₂CH₂CH₂CH₂Si), 17.89 (s, CF₂CH₂CH₂CH₂Si), 34.30 (t, J 22.07Hz, CF₂CH₂CH₂CH₂Si), 107.63-121.22 (m, (CF₂)₈);

²⁹Si NMR (CDCl₃, in ppm): −20.02 (s, Me₂Si(O—)₂), 7.11 (s, CH₂SiMe₂O—);

GPC M_(n)=7600, M_(w)=13800;

Polydispersity=1.8;

TGA (10° C./min. in air): 302° C. (onset of mass loss), 366° C. (50%mass loss), residue 1.2% at 900° C.; and

DSC (10° C./min. in N₂): two melting peaks were observed at −2.9° C. andat 48.9° C.

Example 13 Synthesis of telechelic diallyl poly(perfluorinatedalkane-dimethylsiloxane)CH₂═CHCH₂[C₆F₁₂C₃H₆(SiMe₂O)_(n′)SiMe₂C₃H₆]_(n)C₆F₁₂CH₂CH═CH₂ from4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorododeca-1,11-diene andhydride-terminated polydimethylsiloxane

CH₂═CHCH₂(CF₂)₆CH₂CH═CH₂ (0.554 g, 1.45 mmol by 100% purity) was weighedinto a round-bottomed flask equipped with a cooling condenser.Hydride-terminated polydimethylsiloxane (DMS-H03 purchased from Gelest,1 g, SiH 2.9 mmol calculated from ¹H NMR) was added followed by 1 mL ofanhydrous THF and 0.0060 g of Karstedt's catalyst (˜2%platinum-divinyltetramethyl-disiloxane complex in xylene). The flask wasflushed with nitrogen for several sec. The mixture was reacted at RT for1 hr, and then in an oil bath at 50° C. overnight. IR showed that a SiHpeak still remained. The reaction was allowed to cool to RT and 0.10 gof CH₂═CHCH₂(CF₂)₆CH₂CH═CH₂ was added followed by 0.0022 g of Karstedt'scatalyst (˜2% platinum-divinyltetramethyl-disiloxane complex in xylene).It was heated to 50° C. in the oil bath for 24 hrs. IR showed thereaction was now complete based on the absence of the Si—H band. Allvolatiles were removed using a rotary evaporator. The resulting viscousoil was washed with anhydrous acetonitrile (5×5 mL) and dried in arotary evaporator and then further dried under vacuum for 24 hrs. Theyield was 0.84 g. Its spectral data were as follows:

IR on KBr disc (selected peaks in cm⁻¹): 2962, 2908, 1644, 1464, 1439,1413, 1322, 1261, 1261, 1202, 1140, 1092, 801, 706, 692. The SiH bandwas absent.

Example 14 Preparation of crosslinked network fromHBP-allyl[(CF₂)₆]—[SiMe₂C₂H₄Si(OEt)₃]

HBP—[(CF₂)₆]—[SiMe₂C₂H₄Si(OEt)₃] (0.2 g) and 10% Sn(II) catalyst (0.2 ghexane solution that had 10% [bis(2-ethylhexanoate) tin] purchased fromGelest) were mixed using a Vortex Mixer and cast on glass micro slidesby wire-wound lab rods (wire size #2.5) made by Paul N. Gardner Company.The coatings were cured in an oven at 120° C. for 7 days. The resultingcoatings were transparent and clear. The advancing contact angle ofwater on the coating was 97°.

Example 15 Comparison of Networks from Hyperbranched(Perfluorocarbon/Siloxane) and Hyperbranched PolycarbosiloxaneCrosslinked with Telechelic Divinyl Polydimethylsiloxane (Comparative)

To a solution of 3.6 g of vinyl-terminated polydimethylsiloxane (GelestDMS-V52) and 0.9 g of HBP—(SiOEt)—(SiMe₂H) orHBP-allyl[(CF₂)_(n)]—(SiMe₂H) (n=4, 6) in 15 mL of heptane was added 0.3mL of 3-methyl-1-pentyn-3-ol hexane solution (0.2 g/ml).HBP—(SiOEt)-(SiMe₂H) was a hyperbranched polymer prepared byhydrosilylation of divinyltetraethoxyldisiloxane andtetrakisdimethylsiloxysilane, as described in the U.S. Pat. No.6,646,089. The mixtures were agitated by a Burrell Wrist-Action shakerat setting 9 for 5 mins. Silicon dioxide (2.47 g) [amorphous,hexamethyldisilazane-treated, particle size 0.02 μm (Gelest SIS6962.0)]was added. The mixtures were vigorously mixed for 7 min. by anUltra-Turrax T8 Homogenizer that uses Rotor/Stator Generator S8N-5 g andfurther agitated by the Burrell Wrist-Action shaker at setting 9 for 5mins. The mixing process using the Ultra-Turrax T8 Homogenizer (7 min.)and Burrell Wrist-Action shaker (5 min.) was repeated and an additionalfinal mixing by the Ultra-Turrax T8 Homogenizer for 7 mins. wasconducted. 0.2 mL of the catalyst Pt-complex hexane solution (0.1 gGelest SIP683 in 1 mL hexane) was added, and the mixtures were shaken bythe Burrell Wrist-Action shaker at setting 9 for 5 min. The formulationswere poured into a plastic cup, in which a pedestal was placed on thebottom, dried overnight at RT, and further cured for 24 hrs in an ovenat 65° C. The plastic cups were removed and the edges of the coatingswere trimmed. The coatings water contact angles were determined usingDuPont Teflon Tape MIL-SPEC-T277 3A as a control and the test resultsare shown in FIG. 1. The water contact angle of the coating fromhyperbranched polycarbosiloxane was clearly lower than that from thecoating containing hyperbranched poly(perfluorocarbon/siloxane),indicating that the latter was significantly more hydrophobic.

The TGA traces (10° C./min. in air) of network coatings fromHBP—(SiOEt)-(SiMe₂H) with polydimethylsiloxane andHBP-allyl[(CF₂)₄]—(SiMe₂H) with polydimethlsiloxane are shown in FIG. 2.The results showed that even with as low as 20 wt % of fluorinatedHBP-allyl[(CF₂)₆]—(SiMe₂H) of Example 5 the thermal stability of network(5% weight loss at 387° C.) was improved in comparison to thenon-fluorinated polycarbosiloxane hyperbranched polymer formulations (5%weight loss at 372° C.).

Example 16 Networks from Hyperbranched Poly(Perfluorocarbon/Siloxane)Crosslinked with Telechelic Diallyl Poly(Fluorocarbon/Siloxane)

Linear CH₂═CHCH₂[C₆F₁₂C₃H₆(SiMe₂O)₂SiMe₂C₃H₆]_(n)C₆F₁₂CH₂CH═CH₂ (0.9 g)(of Example 11) was combined with 0.225 g ofHBP(Allyl)-[(CF₂)₆]—(SiMe₂H) (of Example 5) in 3.5 mL of heptane and0.15 mL of 3-methyl-1-pentyn-3-ol hexane solution (0.20 g/mL). A BurrellWrist-Action shaker at setting 9 for 5 mins. was used to agitate thesolution. Then 0.62 g of Gelest silica (20 nm, HMDS treated) was added,and the mixture was vigorously mixed for 20 mins. using an Ultra-TurraxT8 Homogenizer to disperse the silica. Then 0.10 mL of Pt-complex hexanesolution (Gelest SIP 6831 dissolved in hexane at 0.1 g/mL) was added andagitated by the Burrell Wrist-Action shaker at setting 9 for 5 min. Theresulting solution was cast into a mold. The solvent was allowed toevaporate at RT and the resulting film was cured at 70° C. overnight.The water contact angle of the film was 117° and the methylene iodidecontact angle was 94°.

The time-dependence of the methylene iodide contact angle of anon-fluorinated HBP—(SiOEt)-(SiMe₂H) formulation was compared with thatof the fluorinated HBP as shown in FIG. 3. Both networks had similarinitial contact angles, but that of non-fluorinated polycarbosiloxanecatastrophically decreased after about 30 sec., while that of thefluorinated one remained practically unchanged. This indicated that thelatter had considerably more stable oleophobicity than the former.

Although the invention has been described with reference to itspreferred embodiments, those of ordinary skill in the art may, uponreading and understanding this disclosure, appreciate changes andmodifications which may be made which do not depart from the scope andspirit of the invention as described above or claimed hereafter.

What is claimed is:
 1. Hyperbranched copolymer networks which comprisehyperbranched copolymers containing perfluorocarbon and organosiliconentities that have high hydrophobicity as shown by the water contactangle of the network surface in the range of about 95° to about 135°,and/or high oleophobicity as shown by the CH₂I₂ contact angle of thenetwork surface of >90°, and/or high thermal stability as shown by lackof degradation below 250° C., and/or a glass transition temperature isin the range from about −120° C. to about 25° C., and/or good adhesionto substrates, and/or any combinations thereof, and the networks shouldexhibit chemical resistance.
 2. The hyperbranched copolymers of claim 1wherein the hyperbranched copolymer is soluble before crosslinking andis readily processed.
 3. The hyperbranched copolymers of claim 1 whichare devoid of polar groups.
 4. The hyperbranched copolymers of claim 1containing reactive functional end-groups wherein they are crosslinkableby light, heat, moisture, radiation, catalysis, or chemical reactionwith an appropriate crosslinking reagent.
 5. A process for preparinghyperbranched copolymer networks as claimed in claim 1, which comprisescrosslinking hyperbranched copolymers having perfluorocarbon andorganosilicon entities with a variety of crosslinking agents to formeither rigid or elastomeric networks.
 6. The process of claim 5 whereinthe crosslinking agent is a linear telechelic diallyl(perfluorinatedalkane-dimethylsiloxane) copolymer of the following formula:CH₂═CHCH₂[(CF₂)_(n′)C₃H₆(SiMe₂O)_(n″)SiMe₂C₃H₆]_(n)(CF₂)_(n′)CH₂CH═CH₂wherein: n=degree of polymerization of the copolymer; n′=4, 6 or 8; andn″≧1.
 7. The process of claim 5 wherein the crosslinking agent is alinear (perfluorinated alkane-dimethylsiloxane) copolymer of thefollowing formula:H(SiMe₂O)_(n″)SiMe₂[C₃H₆(CF₂)_(n′)C₃H₆(SiMe₂O)_(n″)SiMe₂]_(n)H wherein:n=degree of polymerization of the copolymer; n′=4, 6 or 8; and n″≧1. 8.A process for preparing hyperbranched copolymers of claim 1 whichcomprises reacting an organosilicon monomer containing —SiR₁R₂H groups,where R₁ and R₂ are independently alkyl, alkoxyl or H, and aperfluoroalkane containing allyl or vinyl functionalities, wherein thenumber of SiH or allyl (vinyl) functionalities must be equal to orgreater than 2 and one must be equal to or greater than
 3. 9. A processfor preparing hyperbranched copolymers of claim 1 which comprisesreacting organosilicon monomers containing vinyl or allylfunctionalities, and perfluoroalkane monomers containing —SiR₁R₂Hgroups, where R₁ and R₂ are alkyl, alkoxyl or H, wherein the number ofSiH or allyl (vinyl) functionalities must be equal to or greater than 2and one must be equal to or greater than
 3. 10. A process for preparinghyperbranched copolymers of claim 1 whenever prepared from organosiliconmonomers containing —SiR₁R₂H groups, where R₁ and R₂ are alkyl, alkoxylor H, and perfluoroalkane monomers containing vinylether (CH₂═CHO—) orallylether (CH₂═CHCH₂O—) groups, wherein the number of SiH or allyl(vinyl)ether functionalities must be equal to or greater than 2 and onemust be equal to or greater than 3.